DENSITY FUNCTIONAL THEORY INSIGHT INTO Eu(III) AND Am(III) COMPLEXES WITH TWO 2,6-DICARBOXYPYRIDINE DIAMIDE-TYPE LIGANDS
Y. Yang1, Y. Fang2, Q. Liu2, L. Yang1, S. Hu1, S. Hu2, D. Wang3, H. Zhang2, S. Luo1
1China Academy of Engineering Physics, Mianyang, Sichuan, P. R. China
2Beijing Normal University, Beijing, P. R. China
3Sichuan University, Chengdu, P. R. China
Keywords: density functional theory, second order Moller-Plesset perturbation theory, selective extraction, natural bond orbital analysis
Abstract
Extraction complexes of Eu(III) and Am(III) with two 2,6-dicarboxypyridine diamide-type ligands L-A and L-B (Fig. 1) are studied by density functional theory (DFT). At both B3LYP/6-31G(d)/RECP and MP2/6-31G(d)/RECP levels of theory, the geometrical optimizations of the structures of the complexes can achieve the same accuracy and obtain the same geometrical configuration. At the B3LYP/6-311G(d,p)/RECP level of theory Eu3+ and Am3+ prefer to form [ML]3+ complexes under the solvation conditions, and the Am(III) complexes with L-A are more stable than the corresponding Eu(III) complexes. In the system with the ligand L-B, both [ML]3+ and [ML(NO3)3] species are very unstable.
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